CN109054457B - Black pearlescent pigment and preparation method and application thereof - Google Patents
Black pearlescent pigment and preparation method and application thereof Download PDFInfo
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- CN109054457B CN109054457B CN201810767037.5A CN201810767037A CN109054457B CN 109054457 B CN109054457 B CN 109054457B CN 201810767037 A CN201810767037 A CN 201810767037A CN 109054457 B CN109054457 B CN 109054457B
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
- C09C2200/1033—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin comprising an intermediate layer between the core and a stack of coating layers having alternating refractive indices
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/20—Interference pigments comprising a layer with a concentration gradient or a gradient of the refractive index
- C09C2200/205—Interference pigments comprising a layer with a concentration gradient or a gradient of the refractive index of coloured inorganic materials
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- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/402—Organic protective coating
- C09C2200/407—Organosilicon materials, e.g. silanes, silicones
- C09C2200/408—Organosilicon materials, e.g. silanes, silicones comprising additional functional groups, e.g. –NH2, -C=C- or -SO3
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- C09C2220/00—Methods of preparing the interference pigments
- C09C2220/10—Wet methods, e.g. co-precipitation
- C09C2220/106—Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment
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Abstract
The invention provides a black pearlescent pigment and a preparation method and application thereof, relating to the technical field of pearlescent pigments, wherein the black pearlescent pigment sequentially comprises the following components from inside to outside: the color film comprises a pigment base material, an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer. In the black pearlescent pigment, indium oxide is firstly coated to serve as a crystal guide agent, and then a substrate is alternately coated with a high-refraction ferric oxide layer and a low-refraction cobalt oxide layer. The coating layer of the pearlescent pigment is designed into a multi-layer interface structure, so that the reflection and refraction of light can be effectively increased, the brightness and the chromaticity are enhanced, the high-flicker effect is achieved, and meanwhile, the indium oxide added as a crystal guide agent can enable the pigment to form crystals with regular and uniform structures, so that the pearlescent pigment has the effect of high temperature resistance. Therefore, compared with the existing black pearlescent pigment, the black pearlescent pigment has the advantages of higher blackness and brightness, high temperature resistance and high flashing.
Description
Technical Field
The invention relates to the technical field of pearlescent pigments, in particular to a black pearlescent pigment and a preparation method and application thereof.
Background
Pearlescent pigments are increasingly widely used in the application fields of conventional organic, inorganic and metallic pigments as a new pigment. Based on the structural characteristics of the pearlescent pigment, the pearlescent pigment not only has the color of the traditional inorganic organic pigment, but also has a certain luster effect of the metal pigment, and customers tend to the pearlescent pigment with high chroma more and more along with market demands. Among the many colors of pigments, black is in great demand.
The black pearlescent pigments currently circulating in the market mainly comprise the following products: first, organic pigments (such as carbon black and the like) and pearlescent pigments are chemically combined or physically adsorbed to form black pearlescent pigments, but the products have the problems that the blackness and the brightness cannot be well matched, the temperature resistance is poor, and color migration is easy. Secondly, a layer of black composite metal oxide (iron-cobalt composite, iron-manganese black, copper-chromium black, copper-iron-manganese black and the like) is coated on the surface of the pearlescent substrate to form black pearlescent. Although such pearlescent pigments are resistant to high temperatures, they are insufficient in blackness and brightness. And thirdly, a layer of ferroferric oxide is coated on the surface of the pearlescent substrate to form the black pearlescent pigment, the black pearlescent pigment has certain brightness and blackness, but the temperature resistance is poor, and the ferroferric oxide is easily converted into iron oxide red under the high-temperature condition. Therefore, the three existing products can only be used in a certain field, and the application range of the black pearlescent pigment is severely limited.
In view of the above, it is necessary and urgent to develop a black pearlescent pigment which can satisfy the requirement of high temperature resistance, has high blackness and brightness, and has a high glittering effect.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a black pearlescent pigment, which has the advantages of higher blackness and brightness, high temperature resistance and high glittering compared with the existing black pearlescent pigments.
The second purpose of the invention is to provide a preparation method of the black pearlescent pigment, which has the advantages of simple preparation process, convenient processing and operation, strong economy and the like, and can be widely applied to the large-scale production of the black pearlescent pigment.
The third purpose of the invention is to provide the application of the black pearlescent pigment, and the black pearlescent pigment can be widely applied to the preparation of coatings, paints, plastics, leather or wallpaper.
The invention provides a black pearlescent pigment, which sequentially comprises the following components from inside to outside: the color film comprises a pigment base material, an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer;
the thickness of the indium oxide layer is 2-10 nm;
the thickness of the first ferric oxide layer is 50-200 nm;
the thickness of the first cobalt oxide layer is 5-30 nm;
the thickness of the second ferric oxide layer is 20-100 nm;
the thickness of the second cobalt oxide layer is 5-30 nm.
Further, a silicon-doped cobalt oxide layer is further included between the first cobalt oxide layer and the second ferric oxide layer;
the thickness of the silicon-doped cobalt oxide layer is 100-300 nm.
Further, the silicon-doped cobalt oxide layer is composed of cobalt oxide doped with silicon dioxide.
Further, the pigment substrate is one of natural mica, synthetic mica, glass or flaky alumina;
preferably, the pigment base material is synthetic mica with the particle size of 1-100 mu m;
more preferably, the synthetic mica is fluorophlogopite.
Further, the black pearlescent pigment optionally further comprises an outer protective layer, and the outer protective layer is coated on the second cobalt oxide layer.
Further, the outer protective layer is an organosilane coupling agent layer;
preferably, the thickness of the organosilane coupling agent layer is 5-25nm, and the dosage of the organosilane coupling agent accounts for 1-5% of the total weight of the black pearlescent pigment.
Further, the organosilane coupling agent is gamma-glycidoxypropyltrimethoxysilane.
The invention provides a preparation method of a black pearlescent pigment, which comprises the following steps:
firstly, adding water into a pigment base material to prepare slurry, then sequentially coating an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a silicon-doped cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer on the pigment base material by a hydrolysis coating method according to the layer sequence of the black pearlescent pigment from inside to outside, and then optionally coating an outer protective layer to obtain the black pearlescent pigment.
Further, the pH value of the indium oxide layer, the first ferric oxide layer and the second ferric oxide layer which are coated by hydrolysis is 2-4;
the pH value of the hydrolytic coating of the first cobalt oxide layer, the silicon-doped cobalt oxide layer and the second cobalt oxide layer is 7-10.
The invention provides an application of the black pearlescent pigment in preparation of coatings, paints, plastics, leather or wallpaper.
Compared with the prior art, the invention has the beneficial effects that:
the black pearlescent pigment provided by the invention sequentially comprises the following components from inside to outside: the color film comprises a pigment base material, an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer. In the black pearlescent pigment, indium oxide is firstly coated to serve as a crystal guide agent, and then a substrate is alternately coated by a high-refraction ferric oxide layer and a low-refraction cobalt oxide layer, so that the black pearlescent pigment is obtained. The coating layer of the black pearlescent pigment is designed into a multi-layer interface structure, so that the reflection and refraction of light can be effectively increased, the brightness and the chromaticity are enhanced, the high-flicker effect is achieved, and meanwhile, the indium oxide added as a crystal guide agent can enable the black pearlescent pigment to form crystals with regular and uniform structures, so that the black pearlescent pigment has the effect of high temperature resistance. Therefore, compared with the existing black pearlescent pigment, the black pearlescent pigment has the advantages of higher blackness and brightness, high temperature resistance and high flashing.
According to the preparation method of the black pearlescent pigment, the indium oxide layer, the first ferric oxide layer, the first cobalt oxide layer, the silicon-doped cobalt oxide layer, the second ferric oxide layer and the second cobalt oxide layer are sequentially coated on the pigment substrate by a hydrolysis coating method, so that the black pearlescent pigment with a multilayer structure is prepared. The preparation method has the advantages of simple preparation process, convenient processing operation, strong economy and the like, and can be widely applied to the large-scale production of the black pearlescent pigment.
The black pearlescent pigment provided by the invention can be widely applied to preparation of coatings, paints, plastics, leather or wallpaper.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the present invention, a black pearlescent pigment comprises, in order from inside to outside: the color film comprises a pigment base material, an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer;
the thickness of the indium oxide layer is 2-10 nm;
the thickness of the first ferric oxide layer is 50-200 nm;
the thickness of the first cobalt oxide layer is 5-30 nm;
the thickness of the second ferric oxide layer is 20-100 nm;
the thickness of the second cobalt oxide layer is 5-30 nm.
The black pearlescent pigment provided by the invention sequentially comprises the following components from inside to outside: the color film comprises a pigment base material, an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer. In the black pearlescent pigment, indium oxide is firstly coated to serve as a crystal guide agent, and then a substrate is alternately coated by a high-refraction ferric oxide layer and a low-refraction cobalt oxide layer, so that the black pearlescent pigment is obtained. The coating layer of the pearlescent pigment is designed into a structure with a multilayer interface, so that the reflection and refraction of light can be effectively increased, the brightness and the chromaticity are enhanced, the high-flicker effect is achieved, and meanwhile, the indium oxide added as a crystal guide agent can enable the black pearlescent pigment to form crystals with regular and uniform structures, so that the black pearlescent pigment has the effect of high temperature resistance. Therefore, compared with the existing black pearlescent pigment, the black pearlescent pigment has the advantages of higher blackness and brightness, high temperature resistance and high flashing.
Preferably, the thickness of the first ferric oxide layer is 60-180 nm; the thickness of the first cobalt oxide layer is 10-15 nm; the thickness of the second ferric oxide layer is 30-80 nm; the thickness of the second cobalt oxide layer is 8-20 nm.
In a preferred embodiment of the present invention, a silicon-doped cobalt oxide layer is further included between the first cobalt oxide layer and the second iron oxide layer;
as a preferred embodiment, the present invention uses cobalt oxide doped silica as the intermediate low refractive index cladding layer to produce the unexpected result that the pearlescent pigment obtained by the structure has blue phase black and high glittering effect.
The thickness of the silicon-doped cobalt oxide layer is 100-300 nm.
Preferably, the thickness of the silicon-doped cobalt oxide layer is 150-250 nm.
In the above preferred embodiment, the silicon-doped cobalt oxide layer is composed of cobalt oxide doped with silicon dioxide.
In a preferred embodiment of the present invention, the pigment substrate is one of natural mica, synthetic mica, glass or flake alumina;
preferably, the pigment base material is synthetic mica with the particle size of 1-100 mu m;
more preferably, the synthetic mica is fluorophlogopite. When the synthetic mica is fluorophlogopite, the obtained pigment can obtain good optical effect, and especially when the particle size distribution is narrow (1.5-4.5), the effect is more remarkable. The average particle size of the fluorophlogopite is 5-60 μm, preferably 7-45 μm, and more preferably 10-40 μm.
In a preferred embodiment of the present invention, the black pearlescent pigment further optionally comprises an outer protective layer which is coated on the second cobalt oxide layer.
As a preferred embodiment, the outer protective layer can be used to increase the weatherability of the black pearlescent pigments of the present invention, and is further suitable for use in automotive grade spray paint and in applications where weatherability is required.
In the above preferred embodiment, the outer protective layer is an organosilane coupling agent layer;
preferably, the thickness of the organosilane coupling agent layer is 5-25nm, and the dosage of the organosilane coupling agent accounts for 1-5% of the total weight of the black pearlescent pigment.
In the above preferred embodiment, the organosilane coupling agent is gamma-glycidoxypropyltrimethoxysilane.
Preferably, the preparation method of the outer protective layer comprises the following steps: adding water into the black pearlescent pigment for pulping to obtain pearlescent pigment slurry, heating to 70-90 ℃, adjusting the pH to 8.0-10.0, slowly adding 2-5 wt% of sodium metasilicate pentahydrate (added in the form of aqueous solution) relative to the pearlescent pigment, keeping the pH stable at 8.0-10.0 in the adding process, reducing the pH to 5.0-7.0 after the adding is finished, adding 0.1-0.5 wt% of cerium nitrate and 0.1-0.3 wt% of aluminum nitrate relative to the pearlescent pigment, fully stirring, reducing the pH to 5.0-7.0, adding 1-4 wt% of gamma-glycidyl ether oxypropyltrimethoxysilane and 1-4 wt% of 3-aminopropyltriethoxysilane relative to the pearlescent pigment, fully stirring, filtering, washing and drying to obtain the black pearlescent pigment outer protective layer.
According to one aspect of the present invention, a method for preparing a black pearlescent pigment, the method comprising the steps of:
firstly, adding water into a pigment base material to prepare slurry, then sequentially coating an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a silicon-doped cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer on the pigment base material by a hydrolysis coating method according to the layer sequence of the black pearlescent pigment from inside to outside, and then optionally coating an outer protective layer to obtain the black pearlescent pigment.
According to the preparation method of the black pearlescent pigment, the indium oxide layer, the first ferric oxide layer, the first cobalt oxide layer, the silicon-doped cobalt oxide layer, the second ferric oxide layer and the second cobalt oxide layer are sequentially coated on the pigment substrate by a hydrolysis coating method according to the layer sequence of the black pearlescent pigment from inside to outside, and then an outer protective layer is optionally coated, so that the black pearlescent pigment with a multilayer structure is prepared. The preparation method has the advantages of simple preparation process, convenient processing operation, strong economy and the like, and can be widely applied to the large-scale production of the black pearlescent pigment.
Preferably, the preparation method of the black pearlescent pigment specifically comprises the following steps:
(A) adding water into a pigment base material to prepare slurry;
(B) adding water-soluble indium salt corresponding to indium oxide into the slurry prepared in the step (A), and coating an indium oxide layer by hydrolysis to enable the thickness of the indium oxide layer to be 2-10 nm;
(C) coating an iron sesquioxide layer on the indium oxide layer coated in the step (B) to enable the thickness of the iron sesquioxide layer to be 50-100 nm;
(D) coating the step (C) with soluble cobalt salt corresponding to cobalt oxide in a hydrolysis way to ensure that the thickness of the coating is 5-30 nm;
(E) using a silica layer coated in step (D) by using a soluble silicate corresponding to the oxide with a low refractive index (e.g. sodium silicate or potassium silicate or lithium silicate) and doping a cobalt oxide layer so that it has a thickness of 100-300 nm;
(F) coating the ferric oxide layer on the step (E) by hydrolysis by using a water-soluble ferric salt corresponding to the ferric oxide so that the thickness of the ferric oxide layer is 20-100 nm;
(G) coating soluble cobalt salt corresponding to the cobalt oxide on the step (F) in a hydrolysis way to ensure that the thickness of the cobalt salt is 5-30 nm;
optionally, (H) coating an organosilane coupling agent layer having a thickness of 5 to 25nm with an organosilane coupling agent on the ferric oxide layer coated in step (G);
(I) filtering, washing, drying and high-temperature calcining the material obtained after the step (G) or the step (H).
Preferably, the drying temperature in the step (I) is 100-150 ℃, and more preferably 110-120 ℃; the temperature of the high-temperature calcination in the step (I) is 700-850 ℃, and is more preferably 760-800 ℃.
In a preferred embodiment of the present invention, the indium oxide layer, the first ferric oxide layer and the second ferric oxide layer are coated by hydrolysis, and the pH value is 2 to 4; the pH value of the hydrolytic coating of the first cobalt oxide layer, the silicon-doped cobalt oxide layer and the second cobalt oxide layer is 7-10.
Namely, the pH value of the hydrolytic coating in the steps (B), (C) and (F) is 2 to 4, and the pH value of the hydrolytic coating in the steps (D), (E) and (G) is 7 to 10.
Preferably, the water-soluble indium salt is an indium oxide solution; the water-soluble ferric salt is one of ferric chloride, ferric nitrate or ferric sulfate solution; the water-soluble cobalt salt is one of cobalt chloride, cobalt nitrate or cobalt sulfate solution.
According to one aspect of the invention, the use of the black pearlescent pigment described above for the preparation of coatings, paints, plastics, leather or wallpaper.
The black pearlescent pigment provided by the invention can be widely applied to preparation of coatings, paints, plastics, leather or wallpaper.
The technical solution of the present invention will be further described with reference to the following examples.
Example 1
100g of fluorophlogopite having a particle size in the range from 5 to 45 μm (average particle size 27 μm) are added with stirring to 2L of soft water and heated to 80 ℃ and the pH is adjusted to 3.0 with 1:1 hydrochloric acid, 200ml of 5% indium trichloride solution are then metered in slowly and the pH is kept constant with 30% sodium hydroxide solution,
after the addition, the slow metering of 900ml of 10% iron trichloride solution was continued, during which the pH was kept constant with 30% sodium hydroxide solution, and after the pH had been raised to 8.0, 200ml of 5% cobalt chloride solution were slowly metered in, while the pH was controlled and maintained at 8.0 with 30% sodium hydroxide;
after the addition is finished, stirring for half an hour, reducing the pH value to 3.0 by using 1:1 hydrochloric acid, slowly adding 900ml of 10% ferric trichloride solution, keeping the pH value constant by using 30% sodium hydroxide solution,
after the addition has been completed, stirring is continued for half an hour, after which the pH is raised to 8.0, 200ml of 5% cobalt chloride solution are slowly metered in, while the pH is kept constant at 8.0 and is controlled with 30% sodium hydroxide,
and after the addition is finished, continuing stirring for half an hour, filtering, washing, drying at 110 ℃ for 12 hours, and finally calcining at 760 ℃ for 0.5 hour to obtain the blue-phase black pearlescent pigment.
The thickness of each coating layer of the blue-phase black pearlescent pigment is as follows in sequence: (c) the thickness of the ferric oxide layer is 75 nm; (d) the thickness of the cobalt oxide layer is 15 nm; (f) the thickness of the ferric oxide layer is 60 nm; (h) the thickness of the cobalt oxide layer was 15 nm.
Example 2
100g of fluorophlogopite having a particle size in the range from 5 to 45 μm (average particle size 27 μm) are added with stirring to 2L of soft water and heated to 80 ℃ and the pH is adjusted to 3.0 with 1:1 hydrochloric acid, 200ml of 5% indium trichloride solution are then metered in slowly and the pH is kept constant with 30% sodium hydroxide solution,
after the addition, the slow metering of 900ml of 10% iron trichloride solution was continued, during which the pH was kept constant with 30% sodium hydroxide solution, and after the pH had been raised to 8.0, 200ml of 5% cobalt chloride solution were slowly metered in, while the pH was controlled with 30% sodium hydroxide and was kept constant at 8.0.
After stirring for a further half an hour after the addition, 500ml of 20% sodium silicate solution are slowly metered in at this pH while the pH is controlled and maintained at 8.0 with 5% cobalt chloride solution.
After the addition is finished, stirring for half an hour, reducing the pH value to 3.0 by using 1:1 hydrochloric acid, slowly adding 900ml of 10% ferric trichloride solution, keeping the pH value constant by using 30% sodium hydroxide solution,
after the addition has been completed, stirring is continued for half an hour, after which the pH is raised to 8.0, 200ml of 5% cobalt chloride solution are slowly metered in, while the pH is kept constant at 8.0 and is controlled with 30% sodium hydroxide,
and after the addition is finished, continuing stirring for half an hour, filtering, washing, drying at 110 ℃ for 12 hours, and finally calcining at 760 ℃ for 0.5 hour to obtain the blue-phase black pearlescent pigment.
The thickness of each coating layer of the blue-phase black pearlescent pigment is as follows in sequence: (c) the thickness of the ferric oxide layer is 75 nm; (d) the thickness of the cobalt oxide layer is 15 nm; (e) the thickness of the silicon-doped cobalt oxide layer is 180nm (f), and the thickness of the ferric oxide layer is 60 nm; (h) the thickness of the cobalt oxide layer was 15 nm.
Example 3
The black pearlescent pigment obtained in example 2 was coated with an outer protective layer.
Adding water into 100g of pearlescent pigment for pulping, adding water to 666ml, heating to 78 ℃, and calling liquid alkali to slowly rise the pH: 9.0, 60mL of 5% sodium metasilicate pentahydrate solution, flow: 0.5mL/min, pH controlled with 5% tartaric acid: 9.0.
after the addition of 1.5mol of hydrochloric acid, the flow rate: 0.6mL/min to reduce the pH to 6.5, adding 1.0g of 20.2% Ce (NO3)3,3.5g of 4.3% Al (NO3) 39H 2O, stirring for 15min, adjusting the pH to 6.5, adding 2.0g of gamma-glycidoxypropyltrimethoxysilane and 2.0g of 3-aminopropyltriethoxysilane, stirring for 1 hour, filtering, washing and drying.
The obtained sample is suitable for the application fields of automobile-grade spray paint and weather-resistant requirements.
Experimental example 1
The samples obtained in examples 1 and 2 and a commercially available KC11402 black pearlescent pigment were subjected to quality evaluation by a common method of coating a scratch card or a spray plate. Adding a certain pearlescent pigment into resin or paint, stirring uniformly, coating or spraying a plate, and testing the color and the smoothness by using an X-Rite MA68 color difference instrument. As shown in the following table:
the samples prepared in the examples 1 and 2 of the invention have similar hue (h DEG represents hue), and the color saturation (C value) and the brightness (L value) with the existing product KC11402, and especially the black pearlescent pigment containing the silicon-doped cobalt oxide layer in the example 3 has very obvious improvement of the color saturation equivalent and more sufficient blue phase.
Example 4: paint spraying application
Accurately weigh 4.00 grams of the pearlescent pigment of example 3, add 4.0 grams of butyl acetate and 8.0 grams of polyester automotive coating resin, place under a stirrer and stir for 10 minutes, continue to add 84.0 grams of the automotive coating resin system and stir for 5 minutes. The viscosity of the coating was adjusted to 14-15 seconds for Ford 4 cup before spraying. And during spraying, the temperature of a spraying room is controlled to be 25 ℃, and the relative humidity is controlled to be 60%. Spraying twice, flashing for 10 minutes, covering with varnish, flashing again, and baking at 140 ℃ for 30 minutes.
Example 5: injection molding applications
200 g of polypropylene (PP) material dried at 105 ℃ is accurately weighed into a plastic sealing bag, 1 ml of gloss oil (also called dispersing oil) is added, and then the mixture is shaken to fully mix the gloss oil and the polypropylene material. 4.000 g of the pearl essence of example 2 was weighed into a plastic sealed bag using an analytical balance, and the bag was shaken and kneaded again to disperse the pearl essence uniformly and thoroughly in the PP pellets. After the temperature of the charging barrel reaches a set value (usually 180-200 ℃), adding the prepared polypropylene material into a hopper, extruding the original residual material in the charging barrel by using the functions of injecting glue and melting glue until a new material is extruded, wherein the extruded new material has luster, no impurities, no black spots, no scorching and no bubbles; meanwhile, the nozzle is not blocked during glue injection. After the front and the rear plastic sheets are not different, the produced plastic sheets are stable and qualified products, and can enter automatic normal production.
In conclusion, the coating layer of the black pearlescent pigment is designed into a multi-layer interface structure, so that the reflection and refraction of light can be effectively increased, the brightness and the chromaticity are enhanced, the high-flicker effect is achieved, and meanwhile, the indium oxide added as the crystal guide agent can enable the black pearlescent pigment to form crystals with regular and uniform structures, so that the high-temperature resistant effect is achieved. Therefore, compared with the existing black pearlescent pigment, the black pearlescent pigment has the advantages of higher blackness and brightness, high temperature resistance and high flashing.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (12)
1. The black pearlescent pigment is characterized by comprising the following components in sequence from inside to outside: the color film comprises a pigment base material, an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer;
the thickness of the indium oxide layer is 2-10 nm;
the thickness of the first ferric oxide layer is 50-200 nm;
the thickness of the first cobalt oxide layer is 5-30 nm;
the thickness of the second ferric oxide layer is 20-100 nm;
the thickness of the second cobalt oxide layer is 5-30 nm;
and a silicon-doped cobalt oxide layer is further arranged between the first cobalt oxide layer and the second ferric oxide layer, and the thickness of the silicon-doped cobalt oxide layer is 100-300 nm.
2. The black pearlescent pigment of claim 1, wherein the silicon-doped cobalt oxide layer is comprised of cobalt oxide doped with silica.
3. The black pearlescent pigment of claim 1, wherein the pigment substrate is one of natural mica, synthetic mica, glass or flake alumina.
4. The black pearlescent pigment according to claim 3, wherein the pigment base material is synthetic mica having a particle diameter of 1 to 100 μm.
5. The black pearlescent pigment according to claim 4, wherein the synthetic mica is fluorophlogopite.
6. The black pearlescent pigment according to any one of claims 1-5, wherein the black pearlescent pigment further optionally comprises an outer protective layer coated on the second cobalt oxide layer.
7. The black pearlescent pigment of claim 6, wherein the outer protective layer is an organosilane coupling agent layer.
8. The black pearlescent pigment according to claim 7, wherein the thickness of the organosilane coupling agent layer is 5 to 25nm, and the amount of the organosilane coupling agent is 1 to 5% by weight based on the total weight of the black pearlescent pigment.
9. The black pearlescent pigment of claim 7, wherein the organosilane coupling agent is gamma-glycidoxypropyltrimethoxysilane.
10. A method for preparing a black pearlescent pigment according to any one of claims 1 to 9, characterized in that the method comprises the steps of:
firstly, adding water into a pigment base material to prepare slurry, then sequentially coating an indium oxide layer, a first ferric oxide layer, a first cobalt oxide layer, a silicon-doped cobalt oxide layer, a second ferric oxide layer and a second cobalt oxide layer on the pigment base material by a hydrolysis coating method according to the layer sequence of the black pearlescent pigment from inside to outside, and then optionally coating an outer protective layer to obtain the black pearlescent pigment.
11. The method for preparing a black pearlescent pigment according to claim 10, wherein the pH value of the hydrolyzed coating of the indium oxide layer, the first ferric oxide layer and the second ferric oxide layer is 2 to 4;
the pH value of the hydrolytic coating of the first cobalt oxide layer, the silicon-doped cobalt oxide layer and the second cobalt oxide layer is 7-10.
12. Use of a black pearlescent pigment according to any one of claims 1 to 9 for the preparation of coatings, paints, plastics, leather or wallpaper.
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| CN105705589A (en) * | 2013-10-28 | 2016-06-22 | Cqv株式会社 | Iron oxide based black glossy pigment and method for preparing same |
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| CN105705589A (en) * | 2013-10-28 | 2016-06-22 | Cqv株式会社 | Iron oxide based black glossy pigment and method for preparing same |
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